CN116217909A - Polymerization method of 1, 3-dioxolan-4-one compounds - Google Patents

Polymerization method of 1, 3-dioxolan-4-one compounds Download PDF

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CN116217909A
CN116217909A CN202310237809.5A CN202310237809A CN116217909A CN 116217909 A CN116217909 A CN 116217909A CN 202310237809 A CN202310237809 A CN 202310237809A CN 116217909 A CN116217909 A CN 116217909A
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imidazole
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马海燕
黄哲
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East China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof

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Abstract

The invention provides a polymerization method of a 1, 3-dioxolan-4-ketone compound, which comprises the following steps: the polymerization reaction of 1, 3-dioxolan-4-ketone compound is carried out under the catalysis of imidazole substituted aminophenoxy zinc complex catalyst. The imidazole substituted aminophenoxy zinc complex catalyst has a structure shown in a formula (I), and the preparation method comprises the following steps: the neutral ligand directly reacts with the metal raw material compound in an organic medium, and then the target compound is obtained through the steps of filtering, concentrating and recrystallizing. The 1, 3-dioxolan-4-one compound has a structure shown in a formula (II). Compared with the prior art, the polymerization method provided by the invention enables the 1, 3-dioxolan-4-one compounds to realize homopolymerization and random copolymerization with lactide with high efficiency.

Description

Polymerization method of 1, 3-dioxolan-4-one compounds
Technical Field
The invention relates to the technical field of polymers, in particular to a polymerization method of a 1, 3-dioxolan-4-one compound.
Background
From the birth of plastics to the present, synthetic plastics mainly containing polyolefin are widely used. The petrochemical products are taken as raw materials and are difficult to degrade, so that the energy and environmental problems caused by the wide use of polyolefin materials are increasingly prominent. In order to eliminate white pollution and also to relieve the dependence on petroleum resources, the development of degradable polymer materials has been developed. Among the various degradable materials known at present, the polyester material has the best biocompatibility, most of raw materials are derived from circularly regenerated biomass, and wastes of the raw materials can be naturally degraded into water and carbon dioxide finally, and the water and carbon dioxide return to the whole ecological cycle without additional pollution, so that the material is a green environment-friendly material with great development prospect. For example, the polylactic acid material in the research hot spot in the current academia and industry not only can be completely degraded, but also is heat-resistant, stretch-resistant and easy to process, and is suitable for industrial production. The research on the synthesis is also mature, and the main scheme at present is to synthesize polylactic acid by ring-opening polymerization of lactic acid dimer lactide under the catalysis of a catalyst. The catalyst used in the polymerization reaction is mainly various metal organic catalysts to realize the high isotactic selectivity polymerization or high activity polymerization of the catalytic racemization lactide. The polylactic acid polymer chain structure is single in general, and the post-modification is difficult, so that the application scene is limited, and the research of synthesizing polyester through ring-opening polymerization of other suitable monomers or synthesizing a polyester copolymer through copolymerization with lactide becomes a current research hot spot.
The 1, 3-dioxolan-4-one compounds as the polymerization monomers do not occur too long, and are very specific polymerization monomers independent of hydroxy acids, lactones, lactide, and oxycarboxylic anhydrides. The relevant research literature is very limited, but the advantages are very prominent. The high reactivity of the oxycarboxylic anhydride brings about instability, the monomer is difficult to purify and store, and the synthesis of the oxycarboxylic anhydride also depends on toxic chemicals; compared with oxycarboxylic acid anhydride, the 1, 3-dioxolan-4-one monomer is simpler, safer and faster to synthesize, and the corresponding monomer can be prepared by dehydrating the raw materials only by alpha-hydroxy acid and any aldehyde ketone under the catalysis of acid, so that the method is a polymerized monomer type with a great research prospect.
In 2014, martin and colleagues first use 1, 3-dioxolan-4-one monomer for polymerization, and the feeding ratio of lactide to 1, 3-dioxolan-4-one (DOX) to catalyst and initiator is 250:250:1:1, copolymerization at 100℃for 24 hours, the polymer M obtained n =10000, pdi=1.40, insertion of dox up to 36% and glass transition temperature of polymer 42 ℃. The polymer is more susceptible to degradation than ordinary PLA (Green chem.,2014,16,1768).
In 2017, cairns and co-workers synthesized a series of 1, 3-dioxolan-4-one monomers and tried homo-and co-polymerization of some of the monomers. When two kinds are adoptedThe feed ratio of the 1, 3-dioxolan-4-ketone monomer to the catalyst to the initiator is 50:50:1:1, at 40 ℃, the conversion rate of the two monomers reaches more than 90 percent, M of the polymer n =11100, pdi=2.2. In addition, the authors also tried homopolymerization of 5-methyl-1, 3-dioxolan-4-one (MeDOX) with a feed ratio of 100 under the catalysis of Salen-Al complex: 1: polymerization is carried out for 24 hours at 1, and the monomer conversion rate reaches 81 percent. The polymerization activity of the remaining monomers was far inferior to MeDOX, wherein 500 equivalents of (R) -5-phenyl-1, 3-dioxolan-4-one (R-PhDOX) were melt polymerized at 180℃under the catalysis of Salen-Al for 72h before the conversion reached 55%. The polymerization activity of the monomer is very greatly affected by the substituents on the five-membered ring (polym.chem., 2017,8,2990).
In 2020, gazzotti and its colleagues synthesized two 1, 3-dioxolan-4-one monomers with different substituents from biomass carvacrol and cardanol. The monomer and lactide can realize the copolymerization under the catalysis of various zinc salts and tin salts without solvent, but the copolymerization can only realize the low insertion rate (< 21%) of the 1, 3-dioxolan-4-one monomer, and the molecular weight of the copolymer is reduced to different degrees along with the insertion of the 1, 3-dioxolan-4-one monomer, and the glass transition temperature of the copolymer is reduced (Macromolecules, 2020,53,6420).
Although 1, 3-dioxolan-4-one compounds have many advantages in synthesis, the polymerization results are not ideal from the results reported in the current literature, and the reason is probably that the catalyst type involved in polymerization research is limited by Salen-Al complex, zinc salt, tin salt and the like, and the catalytic activity is poor. In addition, the structure of the compound can influence the polymerization activity, so that in the field of polymerization of 1, 3-dioxolan-4-one compounds, a novel catalyst and a high-activity monomer structure are to be further explored, and further intensive researches are to be carried out on the polymerization of the catalyst and other monomers such as lactide, namely homopolymerization and copolymerization of the catalyst and other monomers.
Disclosure of Invention
The invention aims to provide a polymerization method of a 1, 3-dioxolan-4-one compound.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a polymerization method of a 1, 3-dioxolan-4-ketone compound, which comprises the following steps:
carrying out polymerization reaction on a 1, 3-dioxolan-4-one compound under the catalysis of an imidazole substituted aminophenoxy zinc complex catalyst;
the imidazole-substituted aminophenoxy zinc complex catalyst has a structure shown in a formula (I), and the ligand of the imidazole-substituted aminophenoxy zinc complex catalyst has a structure shown in a formula (II):
Figure BDA0004123037730000021
In the formulas (I) and (II):
the R is 1 、R 2 Independently selected from hydrogen, C 1 ～C 12 Alkyl of straight, branched or cyclic structure, C 7 ～C 20 Mono-or poly-aryl substituted alkyl, and one of halogen;
the R is 3 、R 4 Independently selected from C 1 ～C 6 Alkyl of straight, branched or cyclic structure, C 7 ～C 20 Mono-or poly-aryl substituted alkyl, C 6 ～C 18 Aryl of (a);
said X represents an amino group NR 5 R 6 Wherein R is 5 、R 6 Independently selected from C 1 ～C 6 Alkyl of straight, branched or cyclic structure, trimethylsilyl, triethylsilyl, dimethylhydrosilyl, R 5 And R is 6 May be the same or different.
Preferably, in the formulas (I) and (II), the R 1 、R 2 Independently selected from one of hydrogen, methyl, tertiary butyl, isopropyl phenyl and trityl;
the R is 3 Is one of n-butyl, n-hexyl, cyclohexyl, benzyl or phenyl;
the R is 4 Is one of methyl, benzyl or phenyl;
and X is di (trimethylsilyl) amino.
Preferably, the imidazole-substituted aminophenoxy zinc complex catalyst has one of the structures shown below:
Figure BDA0004123037730000031
the polymerization method is characterized in that the preparation method of the imidazole-substituted aminophenoxy zinc complex shown in the formula (I) comprises the following steps:
Figure BDA0004123037730000041
extracting hydrogen from N-substituted imidazole compounds shown in a formula (III) in an organic medium through N-butyllithium, reacting with N, N-dimethylformamide at a reaction temperature of-78-30 ℃ for 2-72 hours, and collecting 2-aldehyde-N-substituted imidazole shown in a formula (IV) from a reaction product;
Optionally, reacting the 2-aldehyde-N-substituted imidazole shown in the formula (IV) with a primary amine compound in an organic medium to obtain an imine compound shown in the formula (V), wherein the reaction temperature is 60-150 ℃ and the reaction time is 2-72 hours; the imine compound is reduced by sodium borohydride to obtain a secondary amine compound shown in a formula (VI), wherein the reaction temperature is-20-50 ℃ and the reaction time is 8-72 hours;
optionally, reacting a secondary amine compound shown in a formula (VI) with 2-bromomethyl-4, 6-disubstituted phenol shown in a formula (VII) in an organic medium in the presence of an acid-binding agent triethylamine at a reaction temperature of-20 to 50 ℃ for 12 to 72 hours, and collecting an imidazole-substituted aminophenol ligand compound (II) from the reaction product;
optionally, reacting the imidazole-substituted aminophenol ligand compound shown in the formula (II) with a zinc metal raw material compound in an organic medium at a reaction temperature of 0-100 ℃ for 12-96 hours, and collecting a target imidazole-substituted aminophenoxy zinc complex (I) from a reaction product;
substituent R in the preparation method 1 ～R 4 Is consistent with each corresponding group of the imidazole-substituted aminophenol ligand (II) and the metal zinc complex (I) thereof which meet the requirements of the invention;
The zinc metal raw material compound has a general formula of ZnX 2 X is consistent with the corresponding group of the imidazole-substituted aminophenoxy zinc complex (I) which meets the invention; the zinc metal starting compound is preferably bis { di (trimethylsilyl) amino } zinc;
the molar ratio of the imidazole substituted aminophenol ligand compound to the zinc metal raw material compound is 1:1-1.5;
in the preparation method, the organic medium is one or two selected from methanol, tetrahydrofuran, diethyl ether, toluene, benzene, petroleum ether and n-hexane.
The polymerization method is characterized in that the 1, 3-dioxolan-4-one compound has a structure as shown in a formula (VIII):
Figure BDA0004123037730000051
/>
in the formula (VIII):
the R is 7 Independently selected from C 1 ～C 12 Alkyl of straight, branched or cyclic structure, C 7 ～C 20 Mono-or poly-aryl substituted alkyl, C 6 ～C 18 Aryl of (a);
the R is 8 、R 9 Independently selected from C 1 ～C 6 Alkyl groups of straight, branched or cyclic structure, or both are linked to form a ring; r is R 8 And R is 9 May be the same or different;
* The configuration of the carbon atom at which the standard is positioned is R-, S-or racemization structure.
Preferably, said formula (VIII), said R 7 Independently selected from C 1 ～C 6 Alkyl, phenyl, benzyl of straight, branched or cyclic structure;
the R is 8 、R 9 Independently selected from methyl, ethyl, propyl, or a combination thereof Forming five-membered ring and six-membered ring.
More preferably, the 1, 3-dioxolan-4-one compound has a structure represented by the formulas (IX) to (XII):
Figure BDA0004123037730000052
the polymerization method is characterized in that the preparation method of the 1, 3-dioxolan-4-one compound in the formula (VIII) comprises the following steps:
Figure BDA0004123037730000053
dehydrating and cyclizing the substituted alpha-hydroxycarboxylic acid and the ketone compound in the presence of a dehydrating agent, wherein the reaction temperature is-25-160 ℃, the reaction time is 1-72 hours, and collecting the 1, 3-dioxolan-4-ketone compound shown as a formula (VIII) from a reaction product;
substituent R in the preparation method 7 ～R 9 Is consistent with each corresponding group of the 1, 3-dioxolan-4-one compound (VIII) which satisfies the present invention.
The polymerization method is characterized in that the raw material of the polymerization reaction also comprises lactide as a comonomer;
preferably, the lactide is one or more of L-lactide, D-lactide, rac-lactide and meso-lactide.
The polymerization method is characterized in that the ratio of the imidazole-substituted aminophenoxy zinc complex catalyst to the mass of the 1, 3-dioxolan-4-one compound is preferably 1 (50-1000); the ratio of the imidazole-substituted aminophenoxy zinc complex catalyst to the amount of material of lactide is preferably 1 (0-1000);
Preferably, the temperature of the polymerization reaction is 25-160 ℃;
the time of the polymerization reaction is 0.1 to 200 hours;
the polymerization reaction is carried out under an inert atmosphere.
Preferably, the raw materials for the polymerization reaction further comprise alcohol compounds;
the ratio of the imidazole substituted aminophenoxy zinc complex catalyst to the mass of the alcohol compound is 1 (0-10);
the alcohol compound is C 1 ～C 10 Alkyl alcohols of linear, branched or cyclic structure, or C 7 ～C 20 Monoaryl-substituted or polyaryl-substituted alkyl alcohols.
The invention provides a polymerization method of a 1, 3-dioxolan-4-ketone compound, which comprises the following steps: the polymerization reaction of 1, 3-dioxolan-4-ketone compound is carried out under the catalysis of imidazole substituted aminophenoxy zinc complex catalyst. Compared with the prior art, the polymerization method provided by the invention enables the 1, 3-dioxolan-4-one compound to carry out homopolymerization and random copolymerization with lactide with higher efficiency.
Detailed Description
The invention provides a polymerization method of a 1, 3-dioxolan-4-ketone compound, which comprises the following steps:
carrying out polymerization reaction on a 1, 3-dioxolan-4-one compound under the catalysis of an imidazole substituted aminophenoxy zinc complex catalyst;
The imidazole-substituted aminophenoxy zinc complex catalyst has a structure shown in a formula (I), and the ligand of the imidazole-substituted aminophenoxy zinc complex catalyst has a structure shown in a formula (II):
Figure BDA0004123037730000061
in the formulas (I) and (II):
the R is 1 、R 2 Independently selected from hydrogen, C 1 ～C 12 Alkyl of straight, branched or cyclic structure, C 7 ～C 20 Mono-or poly-aryl substituted alkyl, and one of halogen;
the R is 3 、R 4 Independently selected from C 1 ～C 6 Straight chain,Alkyl of branched or cyclic structure, C 7 ～C 20 Mono-or poly-aryl substituted alkyl, C 6 ～C 18 Aryl of (a);
said X represents an amino group NR 5 R 6 Wherein R is 5 、R 6 Independently selected from C 1 ～C 6 Alkyl of straight, branched or cyclic structure, trimethylsilyl, triethylsilyl, dimethylhydrosilyl, R 5 And R is 6 May be the same or different.
Preferably, in the formulas (I) and (II), the R 1 、R 2 Independently selected from one of hydrogen, methyl, tertiary butyl, isopropyl phenyl and trityl;
the R is 3 Is one of n-butyl, n-hexyl, cyclohexyl, benzyl or phenyl;
the R is 4 Is one of methyl, benzyl or phenyl;
and X is di (trimethylsilyl) amino.
Preferably, the imidazole-substituted aminophenoxy zinc complex catalyst has one of the structures shown below:
Figure BDA0004123037730000071
the polymerization method is characterized in that the preparation method of the imidazole-substituted aminophenoxy zinc complex shown in the formula (I) comprises the following steps:
Figure BDA0004123037730000081
Extracting hydrogen from N-substituted imidazole compounds shown in a formula (III) in an organic medium through N-butyllithium, reacting with N, N-dimethylformamide at a reaction temperature of-78-30 ℃ for 2-72 hours, and collecting 2-aldehyde-N-substituted imidazole shown in a formula (IV) from a reaction product;
optionally, reacting the 2-aldehyde-N-substituted imidazole shown in the formula (IV) with a primary amine compound in an organic medium to obtain an imine compound shown in the formula (V), wherein the reaction temperature is 60-150 ℃ and the reaction time is 2-72 hours; the imine compound is reduced by sodium borohydride to obtain a secondary amine compound shown in a formula (VI), wherein the reaction temperature is-20-50 ℃ and the reaction time is 8-72 hours;
optionally, reacting a secondary amine compound shown in a formula (VI) with 2-bromomethyl-4, 6-disubstituted phenol shown in a formula (VII) in an organic medium in the presence of an acid-binding agent triethylamine at a reaction temperature of-20 to 50 ℃ for 12 to 72 hours, and collecting an imidazole-substituted aminophenol ligand compound (II) from the reaction product;
optionally, reacting the imidazole-substituted aminophenol ligand compound shown in the formula (II) with a zinc metal raw material compound in an organic medium at a reaction temperature of 0-100 ℃ for 12-96 hours, and collecting a target imidazole-substituted aminophenoxy zinc complex (I) from a reaction product;
Substituent R in the preparation method 1 ～R 4 Is consistent with each corresponding group of the imidazole-substituted aminophenol ligand (II) and the metal zinc complex (I) thereof which meet the requirements of the invention;
the zinc metal raw material compound has a general formula of ZnX 2 X is consistent with the corresponding group of the imidazole-substituted aminophenoxy zinc complex (I) which meets the invention; the zinc metal starting compound is preferably bis { di (trimethylsilyl) amino } zinc;
the molar ratio of the imidazole substituted aminophenol ligand compound to the zinc metal raw material compound is 1:1-1.5;
in the preparation method, the organic medium is one or two selected from methanol, tetrahydrofuran, diethyl ether, toluene, benzene, petroleum ether and n-hexane.
The polymerization method is characterized in that the 1, 3-dioxolan-4-one compound has a structure as shown in a formula (VIII):
Figure BDA0004123037730000091
/>
in the formula (VIII):
the R is 7 Independently selected from C 1 ～C 12 Alkyl of straight, branched or cyclic structure, C 7 ～C 20 Mono-or poly-aryl substituted alkyl, C 6 ～C 18 Aryl of (a);
the R is 8 、R 9 Independently selected from C 1 ～C 6 Alkyl groups of straight, branched or cyclic structure, or both are linked to form a ring; r is R 8 And R is 9 May be the same or different;
* The configuration of the carbon atom at which the standard is positioned is R-, S-or racemization structure.
Preferably, said formula (VIII), said R 7 Independently selected from C 1 ～C 6 Alkyl, phenyl, benzyl of straight, branched or cyclic structure;
the R is 8 、R 9 Independently selected from methyl, ethyl and propyl, or the two are connected to form a five-membered ring and a six-membered ring.
More preferably, the 1, 3-dioxolan-4-one compound has a structure represented by the formulas (IX) to (XII):
Figure BDA0004123037730000092
the polymerization method is characterized in that the preparation method of the 1, 3-dioxolan-4-one compound in the formula (VIII) comprises the following steps:
Figure BDA0004123037730000093
dehydrating and cyclizing the substituted alpha-hydroxycarboxylic acid and the ketone compound in the presence of a dehydrating agent, wherein the reaction temperature is-25-160 ℃, the reaction time is 1-72 hours, and collecting the 1, 3-dioxolan-4-ketone compound shown as a formula (VIII) from a reaction product;
substituent R in the preparation method 7 ～R 9 And 1, 3-dioxolan-4-one compounds satisfying the present inventionEach corresponding group of (VIII) is identical.
For convenience of description and understanding of the present invention, the four 1, 3-dioxolan-4-one compounds represented by the above formulas (IX) to (XII) are specifically named as (R) -3-phenyl-1, 4-dioxaspiro [4.5] decan-2-one, (R) -3-phenyl-1, 4-dioxaspiro [4.4] nonan-2-one, (R) -2, 2-dimethyl-5-phenyl-1, 3-dioxolan-4-one, (S) -5-benzyl-2, 2-dimethyl-1, 3-dioxolan-4-one, and are abbreviated as NDOX-1, NDOX-2, NDOX-3, NDOX-4, respectively. Wherein NDOX-1 is prepared by dehydration of D-mandelic acid and cyclohexanone at elevated temperature under acid catalysis (J.Am. Chem. Soc.,1981,103 (18): 5414). NDOX-2 is synthesized by dehydration of D-mandelic acid and cyclopentanone at elevated temperature under acid catalysis (Recueil des Travaux Chimiques des Pays-Bas,1992,111 (3): 129). NDOX-3 is prepared by dehydration of D-mandelic acid with acetone at low temperature under acid catalysis (J Organomet chem.,1993,451 (1): 133). NDOX-4 is prepared by diazotizing L-phenylalanine and then mixing with acetone under acid catalysis at low temperature (org. Lett.,2012,14 (16): 4246-4249).
The polymerization method is characterized in that the raw material of the polymerization reaction also comprises lactide as a comonomer;
the lactide is preferably one or more of L-lactide, D-lactide, rac-lactide and meso-lactide.
The mixing sequence of the 1, 3-dioxolan-4-one compound, lactide and imidazole substituted aminophenoxy zinc complex catalyst is not particularly required, and the 1, 3-dioxolan-4-one compound, lactide and imidazole substituted aminophenoxy zinc complex catalyst can be mixed according to any sequence.
In the present invention, the ratio of the amount of the imidazole-substituted aminophenoxy zinc complex catalyst to the amount of the 1, 3-dioxolan-4-one compound is preferably 1 (50 to 1000), more preferably 1 (100 to 500), and most preferably 1 (100 to 200); the ratio of the imidazole-substituted aminophenoxy zinc complex catalyst to the amount of material of the lactide is preferably 1 (0 to 1000), more preferably 1 (0 to 500), most preferably 1 (0 to 200). The invention has no special requirement on the mass ratio of the 1, 3-dioxolan-4-one compound to the lactide, and can meet the requirements on the mass ratio of the catalyst to the 1, 3-dioxolan-4-one monomer and the mass ratio of the catalyst to the lactide. In the present invention, the ratio of the amount of the 1, 3-dioxolan-4-one compound to the lactide can be any value.
In the present invention, the polymerization reaction temperature is preferably 25 to 160 ℃, more preferably 25 to 70 ℃. In the present invention, the time for the copolymerization is preferably 0.1 to 200 hours, more preferably 1 to 80 hours, and most preferably 4 to 24 hours. The heating mode of the polymerization reaction is not particularly required, and the polymerization reaction is heated by adopting a heating mode well known to a person skilled in the art.
In the present invention, the copolymerization is preferably carried out under an inert atmosphere. The inert atmosphere is not particularly limited in the present invention, and inert atmosphere well known to those skilled in the art may be used, and may be argon.
In the present invention, the raw material for the copolymerization reaction preferably further contains an alcohol compound. In the present invention, the alcohol compound is preferably C 1 ～C 10 Alkyl alcohols of linear, branched or cyclic structure, or C 7 ～C 20 Mono-or poly-aryl substituted alkyl alcohols; more preferably isopropanol or benzyl alcohol. In the present invention, the ratio of the amount of the imidazole-substituted aminophenoxy zinc complex catalyst to the amount of the substance of the alcohol compound is preferably 1 (0 to 10), more preferably 1 (0 to 5), and most preferably 1 (0 to 2). The invention has no special requirement on the addition sequence of the alcohol compounds, and can be mixed with the 1, 3-dioxolan-4-ketone compounds, lactide and the catalyst in any sequence. In the invention, the alcohol compound is used as a co-initiator, so that the polymerization rate can be accelerated, the molecular weight of the homopolymer and the copolymer is closer to a theoretical value, the molecular weight distribution is narrower, and the alcohol compound is used for reacting with a catalyst to generate an alkoxy zinc complex in situ, and further catalyze the homopolymerization and copolymerization reaction.
In the present invention, the raw material for the polymerization preferably further comprises a solvent, and the solvent is preferably one or more of toluene, meta-xylene, ortho-xylene, mesitylene, and trichlorobenzene, and specifically may be one, two, three, four, or five. The invention has no special requirement on the addition sequence of the solvent, and can be mixed with alcohol, lactide, 1, 3-dioxolan-4-ketone compounds and catalyst in any sequence. The present invention preferably dissolves the catalyst in a solvent configured such that the catalyst solvent allows for more controlled addition of the catalyst. In the present invention, the solvent is preferably added in an amount based on the concentration of the catalyst. In the present invention, the molar concentration of the imidazole-substituted aminophenoxy zinc complex catalyst in the solvent is preferably 0.020 to 0.030M; more preferably 0.023 to 0.028M, most preferably 0.025M.
The apparatus used in the polymerization reaction is not particularly limited, and those known to those skilled in the art to satisfy the technical requirements of the present application may be used. In the present invention, the polymerization reaction is preferably carried out in a polymerization bottle.
The present invention preferably terminates the polymerization reaction by adding a chain terminator after the polymerization time has been reached. The type of the chain terminator is not particularly limited, and chain terminators capable of terminating the polymerization of 1, 3-dioxolan-4-one compounds, which are well known to those skilled in the art, may be used, and may be particularly aprotic solvents such as petroleum ether, methylene chloride, n-hexane, tetrahydrofuran, etc. which are commercially available. The amount of the chain terminator is not particularly limited, and the chain terminator can be added according to the conventional technical content in the field.
After the reaction is terminated, the present invention preferably uses a solvent with a large polarity and a low boiling point such as methylene chloride or other chloroform to dissolve the reactants. The method has no special requirement on the dosage of the dichloromethane, and can completely dissolve all reactants.
After the methylene chloride is added and concentrated, the present invention preferably adds alcohols such as methanol, ethanol, isopropanol or benzyl alcohol to precipitate the copolymerization product. The invention has no special requirement on the addition amount of the methanol until the sediment is not increased.
After the polymerization product is precipitated, the polymerization product is preferably dried at 60 ℃ to obtain the target product. The drying embodiment of the present invention is not particularly limited, and the drying may be performed by a drying method of solid materials known to those skilled in the art, and may specifically be vacuum drying (less than 0.1 mmHg). In the present invention, the drying time is preferably 16 to 28 hours, more preferably 20 to 26 hours, and most preferably 24 hours.
The invention provides a polymerization method of a 1, 3-dioxolan-4-ketone compound, which comprises the following steps: the polymerization reaction of 1, 3-dioxolan-4-ketone monomer is carried out under the catalysis of imidazole substituted aminophenoxy zinc catalyst. Compared with the prior art, the polymerization method provided by the invention enables the 1, 3-dioxolan-4-one compound to carry out homopolymerization and random copolymerization with lactide with higher efficiency.
The polymerization method provided by the invention is simple and efficient, and the catalyst has high catalytic activity, wide application range and wide application prospect. The invention is further illustrated by the following examples, but is not limited thereto. The polymerization method of 1, 3-dioxolan-4-one compounds provided by the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Synthesis of N-methylimidazole substituted secondary amine
Figure BDA0004123037730000121
N-methylimidazole (8.21 g,0.100 mol) was added to a Schlenk flask under the protection of argon, dissolved in 30mL of anhydrous tetrahydrofuran, cooled to-78 ℃, 40mL of N-butyllithium (0.10 mol, 2.50M) was added, stirred for 5-10min, 15mL of N, N-dimethylformamide (about 0.21 mol) was added dropwise, and the mixture was allowed to react at room temperature for 1 hour or more after heat preservation. 50mL of 12M hydrochloric acid is added for quenching, the excess acid is neutralized by 40% sodium hydroxide solution, the pH is adjusted to 10, dichloromethane extraction is carried out, the organic phase is washed once by saturated sodium chloride aqueous solution, and the solvent is dried by anhydrous sodium sulfate and then spun dry to obtain 1-methyl-1-hydrogen-2-aldehyde imidazole, which is orange yellow liquid (7.20 g, yield 52%, purity 80%).
1-methyl-1H-2 aldehyde imidazole (1.25 g, purity 80%, about 10 mmol) was taken in a 100mL eggplant-type bottle, dissolved in 30mL of methanol, benzyl amine (1.07 g,10.0 mmol) was added dropwise, then a spoon of anhydrous magnesium sulfate was added as a dehydrating agent, the temperature of the oil bath was controlled at 80 ℃, and the mixture was refluxed for 24 hours to obtain a H1-containing mixture, the above reaction apparatus was cooled to room temperature and placed in an ice bath, and sodium borohydride (0.56 g,15 mmol) was added. After no bubbles had formed, the reaction was allowed to proceed to room temperature overnight. The reaction device is placed in an ice bath, 6M dilute hydrochloric acid is added dropwise to quench until no bubbles are generated, dichloromethane is added to extract, and the organic phase is dried by anhydrous sodium sulfate and then spin-dried, so that 1.69g of brown yellow viscous liquid is obtained, which is a crude product of the target product Z1, the purity is about 85%, and the yield is 71%.
The synthesis procedure of Z2 was exactly the same as that of Z1, except that 1-methyl-1-hydro-2-aldehyde-imidazole (1.25 g, purity 80%, about 10 mmol) was used as a raw material, cyclohexylamine (0.99 g,10 mmol), and other operations were the same as the feeding amount of the medicines, to obtain 1.74g of a brown yellow viscous liquid, which was a crude product of the objective product Z2, purity about 89%, yield 80%.
Example 2
Ligand L 1 Synthesis of H
Figure BDA0004123037730000122
To a 100mL eggplant-type bottle was added secondary amine Z1 (0.85 g, purity 85%, about 5.3 mmol), 2mL triethylamine (about 15 mmol), 30mL dichloromethane was added to dissolve, and 2-bromomethyl-4, 6-di-tert-butylphenol (1.59 g,5.30 mmol) was added. The reaction was carried out overnight. The organic phase was dried over anhydrous sodium sulfate and the solvent was dried to give an orange viscous liquid, which was separated out a large amount of white solid by adding methanol, washed with methanol, and removed under reduced pressure to give 1.28g of the product in 57% yield. 1 H NMR(CDCl 3 ,400MHz,298K):δ10.24(br s,1H),7.40–7.23(m,5H),7.21(d, 4 J＝2.4Hz,1H),6.95(d, 3 J＝1.2Hz,1H),6.87(d, 4 J＝2.4Hz,1H),6.79(d, 3 J＝1.3Hz,1H),3.81(s,2H),3.69(s,4H),3.35(s,3H),1.43(s,9H),1.27(s,9H).
Example 3
Ligand L 2 Synthesis of H
Figure BDA0004123037730000131
To a 100mL eggplant-type bottle was added secondary amine Z1 (0.85 g, purity 85%, about 5.30 mmol), 2mL triethylamine (about 15 mmol), 30mL dichloromethane was added to dissolve, and 2-bromomethyl-4-methyl-6-tritylphenol (1.68 g,5.30 mmol) was added and reacted overnight. Washing with saturated saline solution and drying, spin drying the solvent, to give an orange viscous liquid, adding methanol to precipitate a large amount of white solid, washing with methanol, and removing methanol to give 1.67g of the product in 56% yield. 1 H NMR(CDCl 3 ,400MHz,298K):δ10.02(br s,1H),7.25–7.03(m,18H),6.97–6.85(m,4H),6.82(d, 4 J＝2.1Hz,1H),6.68(d, 3 J＝1.3Hz,1H),3.80(s,2H),3.47(s,2H),3.44(s,2H),2.92(s,3H),2.17(s,3H). 13 C NMR(CDCl 3 ,100MHz,298K):δ153.51,146.11(NC＝N),143.42,136.75,133.63,131.29,131.23,131.18,131.00,130.86,130.03,129.89,129.22,129.06,128.46,127.52,127.34,127.01,126.97,125.38,121.90,121.75,121.57,63.23,58.04,57.73,48.29,32.49,20.99.Anal.Calcd.for C 39 H 37 N 3 O:C,83.09；H,6.62；N,7.45.Found:C,83.17；H,6.34；N,7.71％.
Example 4
Ligand L 3 Synthesis of H
Figure BDA0004123037730000132
Into a 100mL eggplant type bottle was added secondary amine Z2 (2.25 g, purity 89%, about 10.40 mmol), 3.04g triethylamine (30.00 mmol), 30mL methylene chloride was dissolved, 2-bromomethyl-4-methyl-6-tritylphenol (3.35 g,10.40 mmol) was added, and the mixture was cooled to room temperatureThe reaction was carried out overnight. Washing with saturated saline solution, drying the organic phase and spin-drying the solvent to obtain an orange viscous liquid, adding methanol to precipitate a large amount of white solid, washing with methanol, and removing methanol to obtain 3.00g of the product with 67% yield. 1 H NMR(CDCl 3 ,400MHz,298K):δ10.36(br s,1H),7.18–7.07(m,15H),6.87–6.84(m,2H),6.73(d, 4 J＝2.1Hz,1H),6.67(d, 3 J＝1.3Hz,1H),3.76(s,2H),3.61(s,2H),3.03(s,3H),2.35(tt,J＝11.9,3.4Hz,1H),2.15(s,3H),1.79–1.71(br d,2H),1.70–1.63(br d,2H),1.63–1.54(br d,1H),1.30–1.16(m,2H),1.15–0.99(m,3H). 13 C NMR(CDCl 3 ,100MHz,298K):δ154.02,146.10,143.85,133.28,131.23,131.17,130.52,130.37,128.72,128.56,127.42,127.23,126.92,126.86,126.62,125.24,121.98,121.74,63.13,58.53,53.60,45.64,32.67,27.34,25.99,21.02.Anal.Calcd.for C 38 H 41 N 3 O:C,82.12；H,7.44；N,7.56.Found:C,82.27；H,7.17；N,7.71％.
Example 5
Synthesis of Zinc Complex Zn1
Figure BDA0004123037730000141
In a 50mL Schlenk flask, bis { di (trimethylsilyl) amino } zinc (3836 mg,1.00 mmol) was added, dissolved in 10mL toluene, and ligand L was added thereto 2 H (563 mg,1.00 mmol) was reacted overnight. Toluene and free silica amine are removed under reduced pressure, a small amount of tetrahydrofuran is added for dissolution, filtration and a proper amount of normal hexane are added for recrystallization, thus obtaining 495mg of white solid with the yield of 63%. 1 H NMR(C 6 D 6 ,400MHz,298K):δ7.73(d, 3 J＝7.5Hz,6H),7.28(d, 4 J＝2.3Hz,1H),7.24(t, 4 J＝7.8Hz,6H),7.17-7.14(m,2H),7.03(t, 3 J＝7.3Hz,3H),7.01–6.94(m,3H),6.02(d, 4 J＝2.3Hz,1H),5.28(d, 3 J＝1.5Hz,1H),5.24(d, 3 J＝1.5Hz,1H),4.30–3.99(m,3H),3.30(d, 2 J＝15.6Hz,1H),2.89(d, 2 J＝11.3Hz,1H),2.64(d, 2 J＝15.5Hz,1H),1.97(s,3H),1.80(s,3H),0.39(s,18H). 13 C NMR(CDCl 3 ,100MHz,298K): 13 C NMR(101MHz,C 6 D 6 )δ165.17(NC＝N),147.87,145.57,134.55,133.11,132.53,132.43,131.58,128.26,128.15,128.02,127.91,127.78,127.67,125.59,124.67,121.93,120.74,119.45,63.91,62.89,60.85,48.09,30.63,20.70,6.22.Anal.Calcd.for C 45 H 54 N 4 OSi 2 Zn:C,68.55；H,6.90；N,7.11.Found:C,68.40；H,7.08；N,7.06％.
Example 6
Synthesis of zinc Complex Zn2
Figure BDA0004123037730000151
In a 50mL Schlenk flask, bis { di (trimethylsilyl) amino } zinc (3836 mg,1.00 mmol) was added, dissolved in 10mL toluene, to which was added ligand L 3 H (555 mg,1.00 mmol) was reacted overnight, after removing toluene and free silamine under reduced pressure, a small amount of tetrahydrofuran was added for dissolution, filtration, and recrystallization with an appropriate amount of n-hexane to give 512mg of a white solid with a yield of 66%. 1 H NMR(400MHz,C 6 D 6 )δ7.72(d, 3 J＝7.5Hz,6H),7.30(d, 4 J＝2.4Hz,1H),7.23(t, 3 J＝7.7Hz,6H),7.01(t, 3 J＝7.3Hz,3H),6.29(d, 4 J＝2.4Hz,1H),5.30(d, 3 J＝1.5Hz,1H),5.10(d, 3 J＝1.5Hz,1H),3.99(d, 2 J＝11.1Hz),2.88(d, 2 J＝15.6Hz,1H),2.86(d, 2 J＝11.1Hz,1H),2.78(tt, 3 J＝11.8Hz,8H),2.70(d, 2 J＝15.6Hz,1H),2.43(br d, 3 J＝11.8Hz,1H),2.18(br d, 3 J＝12.0Hz,1H),2.08(s,3H),2.06(s,3H),1.71(pesudo t, 3 J＝13.2Hz,2H),1.52(br d, 3 J＝13.0Hz,1H),1.30–1.05(m,2H),1.01–0.78(m,3H),0.34(s,18H). 13 C NMR(100MHz,C 6 D 6 )δ165.38,148.07,146.02,134.38,132.61,132.48,131.71,128.43,128.30,128.06,127.82,125.66,125.41,124.92,124.73,122.29,120.74,120.48,119.32,65.73,63.98,58.19,46.44,30.91,30.85,29.28,27.51,26.14,21.04,20.99,6.23.Anal.Calcd.for C 44 H 58 N 4 OSi 2 Zn:C,67.71；H,7.49；N,7.18.Found:C,67.33；H,7.49；N,7.15％.
Example 7
Synthesis of (R) -3-phenyl-1, 4-dioxaspiro [4.5] decan-2-one (NDOX-1)
Figure BDA0004123037730000152
15.20-g D-mandelic acid (100.00 mmol), 12mL of cyclohexanone (116 mmol) and 1.91g of p-toluenesulfonic acid monohydrate (10.00 mmol) are mixed, 100mL of toluene is added as a water carrying agent, water is refluxed at 140 ℃ until no water is distilled out, the reaction is stopped, the mixture is cooled to room temperature, the mixture is washed with saturated sodium bicarbonate aqueous solution for three times, toluene is distilled off, a tan solid is obtained, and 11.2g of colorless solid is obtained after three times of petroleum ether recrystallization, and the yield is 48%. 1 H NMR(400MHz,CDCl 3 ):δ7.51–7.32(m,5H),5.39(s,1H),2.03–1.84(m,4H),1.81–1.66(m,4H),1.61–1.40(m,2H).
Example 8
Synthesis of (R) -3-phenyl-1, 4-dioxaspiro [4.4] nonan-2-one (NDOX-2)
Figure BDA0004123037730000161
15.20-g D-mandelic acid (100.0 mmol), 18mL of cyclopentanone (204.0 mmol) and 1.91g (10.00 mmol) of p-toluenesulfonic acid monohydrate were mixed, 100mL of toluene was added as a water-carrying agent, the mixture was refluxed and water-separated at 140 ℃ to react until no water was distilled off, cooled to room temperature, washed with saturated aqueous sodium bicarbonate solution for three times, toluene was distilled off, and a tan solid was obtained, 10.0g of colorless solid was obtained by recrystallization from ethanol, and the yield was 46%. 1 H NMR(400MHz,CDCl 3 ):δ7.56-7.31(m,5H),5.34(s,1H),2.25-1.97(m,4H),1.95-1.70(m,4H). 13 C NMR(CDCl 3 ,100MHz,298K):δ171.56,134.37,129.08,128.81,126.59,120.90,76.26,37.16,36.85,23.44,21.12.Anal.Calcd.for C 13 H 14 O 3 :C,71.54％；H,6.47％.Found:C,71.61％；H,6.57％.[α] 25 D ＝-62.29(C＝0.0142mol/L,DCM).
Example 9
Synthesis of (R) -2, 2-dimethyl-5-phenyl-1, 3-dioxolan-4-one (NDOX-3)
Figure BDA0004123037730000162
6.30g of concentrated sulfuric acid (about 64.60 mmol) was cooled to-10℃and 10.00. 10.00g D-mandelic acid (65.72 mmol) was dissolved in 30mL of acetone, and the mixture was dropwise added to the concentrated sulfuric acid, followed by reaction at a constant temperature for 1h. 16.70g of sodium carbonate (157.60 mmol) is dissolved in 60mL of water, after the reaction is finished, the mixed solution is slowly poured into the sodium carbonate solution, the solution is continuously stirred until no bubble is generated, suction filtration is carried out, a white solid is obtained, after the solution is redissolved by methylene dichloride, anhydrous sodium sulfate is added for drying and filtration, a small amount of petroleum ether is added for recrystallization after most of methylene dichloride is distilled, and colorless crystals of 6.9g are obtained with the yield of 55%. 1 H NMR(400MHz,CDCl 3 ):δ7.53-7.32(m,5H),5.40(s,1H),1.73(s,3H,CH 3 ),1.68(s,3H,CH 3 ).
Example 10
Synthesis of (S) -5-benzyl-2, 2-dimethyl-1, 3-dioxolan-4-one (NDOX-4)
Figure BDA0004123037730000163
11.90g of concentrated sulfuric acid (ca. 121.40 mmol) are dissolved in 100mL of water, cooled to 0℃and 10.00: 10.00g L-phenylalanine (60.54 mmol) is added and stirred until dissolved. 25.00g of sodium nitrite (362.35 mmol) was dissolved in 60mL of water, and the solution was dropwise added to the aqueous phenylalanine solution. The reaction is carried out for 2h at 0 ℃ and transferred to room temperature for 20h. After the reaction, ethyl acetate is used for extraction for three times, and the yellow solid is obtained after spin drying, and the white solid 7.3g L-3-phenyllactic acid is obtained after washing by methylene dichloride, and the yield is 72.6%.
16.70g of sodium carbonate (157.60 mmol) are dissolved in 60mL of water. 6.30g of concentrated sulfuric acid (about 64.60 mmol) was cooled to minus ten degrees, 10.90g L-3-phenyllactic acid (about 65.60 mmol) was dissolved in 50mL of acetone, and the mixture was added dropwise to the concentrated sulfuric acid, followed by reaction at a constant temperature for 1h. After the reaction is finished, the mixed solution is slowly mixedSlowly pouring into sodium carbonate solution prepared in advance, continuously stirring until no bubbles exist, carrying out suction filtration to obtain white solid, re-dissolving with dichloromethane, adding anhydrous sodium sulfate for drying, adding a small amount of petroleum ether for recrystallization to obtain colorless crystals of 5.6g, and obtaining the yield of 45%. 1 H NMR(400MHz,CDCl 3 ):δ7.48-7.08(m,5H),4.67-4.64(dd, 3 J＝6.5,4.1Hz,1H),3.25–3.00(m,2H),1.50(s,3H),1.36(s,3H).
Example 11
To a polymerization flask, rac-lactide (72 mg,0.5 mmol) and NDOX-1 (116 mg,0.5 mmol) were added under argon and 0.5mL of benzyl alcohol in toluene. 0.5mL of Zn1 in toluene was measured and added to a polymerization flask. So that [ Cat. ] 0 ＝0.005M，[rac-LA]:[NDOX-1]:[Cat.]:[BnOH]=100:100:1:1. Controlling the reaction temperature to 25 ℃, reacting for 6 hours, and adding petroleum ether to terminate the reaction. Dissolving with dichloromethane, sampling, measuring conversion rate, concentrating the residual solution, adding methanol to precipitate polymer, and vacuum drying for 24h. The calculation and the detection show that the lactide conversion rate is 99 percent and the NDOX-1 conversion rate is 15 percent; the lactide chain unit content in the polymer is 93%, and the NDOX-1 chain unit content is 7%; m is M n ＝1.34×10 4 g/mol, molecular weight distribution pdi=1.61.
The M is n And PDI were both detected by GPC.
Example 12
To a polymerization flask, rac-lactide (72 mg,0.5 mmol) and NDOX-1 (116 mg,0.5 mmol) were added under argon and 0.5mL of benzyl alcohol in toluene. 0.5mL of Zn1 in toluene was measured and added to a polymerization flask. So that [ Cat.] 0 ＝0.005M，[rac-LA]:[NDOX-1]:[Cat.]:[BnOH]=100:100:1:1. Controlling the reaction temperature to 45 ℃, reacting for 6 hours, and adding petroleum ether to terminate the reaction. The other processes were the same as in example 11. Lactide conversion was 99% and NDOX-1 conversion was 28%; the lactide chain link content in the polymer is 86 percent, and the NDOX-1 chain link content is 14 percent; m is M n ＝8.28×10 3 g/mol, molecular weight distribution pdi=1.72.
Example 13
To a polymerization flask, rac-lactide (72 mg,0.5 mmol) and NDOX-1 (116 mg,0.5 mmol) were added under argon and 0.5mL of toluene solution was added. Measuring and taking out 0.5mL of Zn1 in toluene was added to the polymerization flask. So that [ Cat.] 0 ＝0.005M，[rac-LA]:[NDOX-1]:[Cat.]:[BnOH]=100:100:1:0. Controlling the reaction temperature to 45 ℃, reacting for 6 hours, and adding petroleum ether to terminate the reaction. The other processes were the same as in example 11. Lactide conversion was 99% and NDOX-1 conversion was 21%; the lactide chain link content in the polymer is 90 percent, and the NDOX-1 chain link content is 10 percent; m is M n ＝1.27×10 4 g/mol, molecular weight distribution pdi=2.05.
Example 14
To a polymerization flask, rac-lactide (72 mg,0.5 mmol) and NDOX-1 (116 mg,0.5 mmol) were added under argon and 0.5mL of toluene solution was added. 0.5mL of Zn1 in toluene was measured and added to a polymerization flask. So that [ Cat.] 0 ＝0.005M，[rac-LA]:[NDOX-1]:[Cat.]:[BnOH]=100:100:1:1. Controlling the reaction temperature at 70 ℃, reacting for 6 hours, and adding petroleum ether to terminate the reaction. The other processes were the same as in example 11. Lactide conversion was 99% and NDOX-1 conversion was 42%; the lactide chain link content in the polymer is 78 percent, and the NDOX-1 chain link content is 22 percent; m is M n ＝6.89×10 3 g/mol, molecular weight distribution pdi=1.81.
Example 15
To a polymerization flask were added rac-lactide (72 mg,0.5 mmol) and NDOX-1 (116 mg,0.5 mmol) under argon and 0.5mL benzyl alcohol in toluene. 0.5mL of Zn2 in toluene was measured and added to a polymerization flask. So that [ Cat.] 0 ＝0.005M，[rac-LA]:[NDOX-1]:[Cat.]:[BnOH]=100:100:1:1. Controlling the reaction temperature to 25 ℃, reacting for 6 hours, and adding petroleum ether to terminate the reaction. The other processes were the same as in example 11. Lactide conversion was 99% and NDOX-1 conversion was 9%; the lactide chain link content in the polymer is 96 percent, and the NDOX-1 chain link content is 4 percent; m is M n ＝1.35×10 4 g/mol, molecular weight distribution pdi=1.86.
Example 16
To a polymerization flask were added rac-lactide (72 mg,0.5 mmol) and NDOX-1 (116 mg,0.5 mmol) under argon and 0.5mL benzyl alcohol in toluene. 0.5mL of Zn2 in toluene was measured and added to a polymerization flask. So that [ Cat.] 0 ＝0.005M，[rac-LA]:[NDOX-1]:[Cat.]:[BnOH]=100:100:1:1. Controlling the reaction temperature 45The reaction is carried out for 6 hours, and petroleum ether is added to terminate the reaction. The other processes were the same as in example 11. Lactide conversion was 99% and NDOX-1 conversion was 17%; the lactide chain unit content in the polymer is 91%, and the NDOX-1 chain unit content is 9%; m is M n ＝9.06×10 3 g/mol, molecular weight distribution pdi=2.05.
Example 17
To a polymerization flask were added rac-lactide (72 mg,0.5 mmol) and NDOX-1 (116 mg,0.5 mmol) under argon and 0.5mL benzyl alcohol in toluene. 0.5mL of Zn2 in toluene was measured and added to a polymerization flask. So that [ Cat.] 0 ＝0.005M，[rac-LA]:[NDOX-1]:[Cat.]:[BnOH]=100:100:1:1. Controlling the reaction temperature at 70 ℃, reacting for 6 hours, and adding petroleum ether to terminate the reaction. The other processes were the same as in example 11. Lactide conversion was 99% and NDOX-1 conversion was 25%; the lactide chain link content in the polymer is 87 percent, and the NDOX-1 chain link content is 13 percent; m is M n ＝5.12×10 3 g/mol, molecular weight distribution pdi=2.50.
Example 18
To a polymerization flask were added rac-lactide (108 mg,0.75 mmol) and NDOX-1 (58 mg,0.25 mmol) under argon and 0.5mL benzyl alcohol in toluene. 0.5mL of toluene solution of Zn2 catalyst was measured and added to a polymerization flask. So that [ Cat. ] 0 ＝0.005M，[rac-LA]:[NDOX-1]:[Cat.]:[BnOH]=150:50:1:1. Controlling the reaction temperature to 45 ℃, reacting for 6 hours, and adding petroleum ether to terminate the reaction. The other processes were the same as in example 11. Lactide conversion was 99% and NDOX-1 conversion was 31%; the lactide chain unit content in the polymer is 95%, and the NDOX-1 chain unit content is 5%; m is M n ＝8.54×10 3 g/mol, molecular weight distribution pdi=3.27.
Example 19
To a polymerization flask were added rac-lactide (130 mg,0.9 mmol) and NDOX-1 (23 mg,0.1 mmol) under argon and 0.5mL benzyl alcohol in toluene. 0.5mL of toluene solution of Zn2 catalyst was measured and added to a polymerization flask. So that [ Cat.] 0 ＝0.005M，[rac-LA]:[NDOX-1]:[Cat.]:[BnOH]=180:20:1:1. Controlling the reaction temperature to 45 ℃, reacting for 6 hours, and adding petroleum ether to terminate the reaction. The other processes were the same as in example 11. Lactide conversion was 99% and NDOX-1 conversion was 36%;the lactide chain link content in the polymer is 98 percent, and the NDOX-1 chain link content is 2 percent; m is M n ＝5.35×10 3 g/mol, molecular weight distribution pdi=4.20.
Example 20
To a polymerization flask were added rac-lactide (72 mg,0.5 mmol) and NDOX-3 (96 mg,0.5 mmol) under argon and 0.5mL benzyl alcohol in toluene. 0.5mL of Zn1 in toluene was measured and added to a polymerization flask. So that [ Cat.] 0 ＝0.005M，[rac-LA]:[NDOX-3]:[Cat.]:[BnOH]=100:100:1:1. Controlling the reaction temperature to 25 ℃, reacting for 6 hours, and adding petroleum ether to terminate the reaction. The other processes were the same as in example 11. Lactide conversion was 99% and NDOX-3 conversion was 22%; the lactide chain link content in the polymer is 90 percent, and the NDOX-3 chain link content is 10 percent; m is M n ＝1.36×10 4 g/mol, molecular weight distribution pdi=1.78.
Example 21
To a polymerization flask, rac-lactide (72 mg,0.5 mmol) and NDOX-3 (96 mg,0.5 mmol) were added under argon and 0.5mL of toluene solution was added. 0.5mL of Zn1 in toluene was measured and added to a polymerization flask. So that [ Cat.] 0 ＝0.005M，[rac-LA]:[NDOX-3]:[Cat.]:[BnOH]=100:100:1:0. Controlling the reaction temperature to 25 ℃, reacting for 6 hours, and adding petroleum ether to terminate the reaction. The other processes were the same as in example 11. Lactide conversion was 99% and NDOX-3 conversion was 2%; the lactide chain link content in the polymer is 99 percent, and the NDOX-3 chain link content is 1 percent; m is M n ＝3.33×10 4 g/mol, molecular weight distribution pdi=2.02.
Example 22
To a polymerization flask, rac-lactide (108 mg,0.75 mmol) and NDOX-3 (48 mg,0.25 mmol) were added under argon and a 0.5mL toluene solution was added. 0.5mL of Zn1 in toluene was measured and added to a polymerization flask. So that [ Cat.] 0 ＝0.005M，[rac-LA]:[NDOX-3]:[Cat.]:[BnOH]=150:50:1:1. Controlling the reaction temperature to 25 ℃, reacting for 6 hours, and adding petroleum ether to terminate the reaction. The other processes were the same as in example 11. Lactide conversion was 99% and NDOX-3 conversion was 35%; the lactide chain unit content in the polymer is 94%, and the NDOX-3 chain unit content is 6%; m is M n ＝6.32×10 3 g/mol, molecular weight distribution pdi=4.22.
Example 23
To a polymerization flask, rac-lactide (72 mg,0.5 mmol) and NDOX-4 (103 mg,0.5 mmol) were added under argon and 0.5mL of a toluene solution of benzyl alcohol was added. 0.5mL of Zn1 in toluene was measured and added to a polymerization flask. So that [ Cat. ] 0 ＝0.005M，[rac-LA]:[NDOX-4]:[Cat.]:[BnOH]=100:100:1:1. Controlling the reaction temperature to 25 ℃, reacting for 6 hours, and adding petroleum ether to terminate the reaction. The other processes were the same as in example 11. Lactide conversion was 99% and NDOX-4 conversion was 30%; the lactide chain link content in the polymer is 87 percent, and the NDOX-4 chain link content is 13 percent; m is M n ＝6.10×10 3 g/mol, molecular weight distribution pdi=3.01.
Example 24
L-lactide (72 mg,0.5 mmol) and NDOX-4 (103 mg,0.5 mmol) were added to a polymerization flask under argon, and 0.5mL of benzyl alcohol toluene solution was added. 0.5mL of Zn1 in toluene was measured and added to a polymerization flask. So that [ Cat.] 0 ＝0.005M，[rac-LA]:[NDOX-4]:[Cat.]:[BnOH]=100:100:1:1. The reaction temperature is controlled to 25 ℃, the reaction is carried out for 50 minutes, and petroleum ether is added to terminate the reaction. The other processes were the same as in example 11. Lactide conversion was 99% and NDOX-4 conversion was 10%; the lactide chain unit content in the polymer is 95%, and the NDOX-4 chain unit content is 5%; m is M n ＝1.55×10 4 g/mol, molecular weight distribution pdi=1.96.
Example 25
To a polymerization flask, rac-lactide (72 mg,0.5 mmol) and NDOX-4 (103 mg,0.5 mmol) were added under argon and 0.5mL of a toluene solution of benzyl alcohol was added. 0.5mL of Zn1 in toluene was measured and added to a polymerization flask. So that [ Cat.] 0 ＝0.005M，[rac-LA]:[NDOX-4]:[Cat.]:[BnOH]=100:100:1:1. Controlling the reaction temperature to 45 ℃, reacting for 6 hours, and adding petroleum ether to terminate the reaction. The other processes were the same as in example 11. Lactide conversion 99%, NDOX-4 conversion 56%; the lactide chain link content in the polymer is 75 percent, and the NDOX-4 chain link content is 25 percent; m is M n ＝5.70×10 3 g/mol, molecular weight distribution pdi=2.98.
Example 26
Under argon, NDOX-4 (206 mg,1 mmol) was added to the flask, followed by 0.5 gmL of benzyl alcohol toluene solution. 0.5mL of toluene solution of catalyst Zn1 was measured and added to a polymerization flask. So that [ Cat.] 0 ＝0.01M，[NDOX-4]＝1M。[NDOX-4]:[Cat.]:[BnOH]=100:1:1. Controlling the reaction temperature at 70 ℃, reacting for 12 hours, and adding petroleum ether to terminate the reaction. The NDOX-4 conversion was 38% as calculated and detected. Polymer number average molecular weight M n ＝4.71×10 3 g/mol, molecular weight distribution pdi=1.52.
Example 27
To a polymerization flask was added NDOX-4 (206 mg,1 mmol) under argon and 0.1mL of benzyl alcohol toluene solution was added. 0.1mL of toluene solution of catalyst Zn1 was measured and added to a polymerization flask. So that [ Cat.] 0 ＝0.01M，[NDOX-4]＝5M。[NDOX-4]:[Cat.]:[BnOH]=100:1:1. Controlling the reaction temperature to be 50 ℃, reacting for 12 hours, and adding petroleum ether to terminate the reaction. The NDOX-4 conversion was 58% as calculated and detected. Polymer number average molecular weight M n ＝4.32×10 3 g/mol, molecular weight distribution pdi=1.86.
Example 28
The procedure of example 27 was repeated except that the reaction temperature was changed to 70℃and the reaction time was changed to 6 hours.
The NDOX-4 conversion was calculated and detected to be 50%. Polymer number average molecular weight M n ＝4.23×10 3 g/mol, molecular weight distribution pdi=1.86.
Example 29
The procedure of example 27 was repeated except that the reaction temperature was changed to 90℃and the reaction time was changed to 6 hours.
The NDOX-4 conversion was 47% as calculated and detected. Polymer number average molecular weight M n ＝3.88×10 3 g/mol, molecular weight distribution pdi=1.71.
Example 30
The procedure of example 27 was repeated except that the reaction temperature was changed to 110℃and the reaction time was changed to 6 hours.
The NDOX-4 conversion was 46% as calculated and detected. Polymer number average molecular weight M n ＝3.70×10 3 g/mol, molecular weight distribution pdi=1.68.
Example 31
To a polymerization flask was added NDOX-4 (206 mg,1 mmol) under argon and 0.1mL of benzyl alcohol toluene solution was added. 0.1mL of toluene solution of Zn2 catalyst was measured and added to a polymerization flask. So that [ Cat.] 0 ＝0.01M，[NDOX-4]＝5M。[NDOX-4]:[Cat.]:[BnOH]=100:1:1. Controlling the reaction temperature to be 50 ℃, reacting for 12 hours, and adding petroleum ether to terminate the reaction. The NDOX-4 conversion was calculated and detected to be 50%. Polymer number average molecular weight M n ＝4.72×10 3 g/mol, molecular weight distribution pdi=1.77.
Example 32
The procedure of example 31 was repeated except that the reaction temperature was changed to 70℃and the reaction time was changed to 6 hours.
The NDOX-4 conversion is 77% through calculation and detection. Polymer number average molecular weight M n ＝3.27×10 3 g/mol, molecular weight distribution pdi=1.75.
Example 33
The procedure of example 31 was repeated except that the reaction temperature was changed to 110℃and the reaction time was changed to 6 hours.
The NDOX-4 conversion was 49% as calculated and detected. Polymer number average molecular weight M n ＝3.63×10 3 g/mol, molecular weight distribution pdi=1.80.
Example 34
To a polymerization flask was added NDOX-4 (206 mg,1 mmol) under argon and 0.1mL of benzyl alcohol toluene solution was added. 0.01mmol of catalyst Zn2 was weighed into a polymerization flask. So that [ NDOX-4 ]]:[Cat.]:[BnOH]=100:1:1. The reaction temperature is controlled at 130 ℃, the reaction is carried out for 6 hours, and petroleum ether is added to terminate the reaction. The NDOX-4 conversion was 94% as calculated and detected. Polymer number average molecular weight M n ＝3.90×10 3 g/mol, molecular weight distribution pdi=1.88.

Claims (10)

1. A polymerization method of 1, 3-dioxolan-4-one compounds, comprising the following steps:
carrying out polymerization reaction on a 1, 3-dioxolan-4-one compound under the catalysis of an imidazole substituted aminophenoxy zinc complex catalyst;
the imidazole-substituted aminophenoxy zinc complex catalyst has a structure shown in a formula (I), and the ligand of the imidazole-substituted aminophenoxy zinc complex catalyst has a structure shown in a formula (II):
Figure FDA0004123037720000011
in the formulas (I) and (II):
the R is 1 、R 2 Independently selected from hydrogen, C 1 ～C 12 Alkyl of straight, branched or cyclic structure, C 7 ～C 20 Mono-or poly-aryl substituted alkyl, and one of halogen;
the R is 3 、R 4 Independently selected from C 1 ～C 6 Alkyl of straight, branched or cyclic structure, C 7 ～C 20 Mono-or poly-aryl substituted alkyl, C 6 ～C 18 Aryl of (a);
said X represents an amino group NR 5 R 6 Wherein R is 5 、R 6 Independently selected from C 1 ～C 6 Alkyl of straight, branched or cyclic structure, trimethylsilyl, triethylsilyl, dimethylhydrosilyl, R 5 And R is 6 May be the same or different.
2. The polymerization process of claim 1 wherein in the formulas (I) and (II), the R 1 、R 2 Independently selected from one of hydrogen, methyl, tertiary butyl, isopropyl phenyl and trityl; the R is 3 Is one of n-butyl, n-hexyl, cyclohexyl, benzyl or phenyl; the R is 4 Is one of methyl, benzyl or phenyl; and X is di (trimethylsilyl) amino.
3. The polymerization process according to claims 1-2, characterized in that the preparation of the imidazole-substituted aminophenoxy zinc complex of formula (I) comprises the steps of:
Figure FDA0004123037720000012
extracting hydrogen from N-substituted imidazole compounds shown in a formula (III) in an organic medium through N-butyllithium, reacting with N, N-dimethylformamide at a reaction temperature of-78-30 ℃ for 2-72 hours, and collecting 2-aldehyde-N-substituted imidazole shown in a formula (IV) from a reaction product;
optionally, reacting the 2-aldehyde-N-substituted imidazole shown in the formula (IV) with a primary amine compound in an organic medium to obtain an imine compound shown in the formula (V), wherein the reaction temperature is 60-150 ℃ and the reaction time is 2-72 hours; the imine compound is reduced by sodium borohydride to obtain a secondary amine compound shown in a formula (VI), wherein the reaction temperature is-20-50 ℃ and the reaction time is 8-72 hours;
Optionally, reacting a secondary amine compound shown in a formula (VI) with 2-bromomethyl-4, 6-disubstituted phenol shown in a formula (VII) in an organic medium in the presence of an acid-binding agent triethylamine at a reaction temperature of-20 to 50 ℃ for 12 to 72 hours, and collecting an imidazole-substituted aminophenol ligand compound (II) from the reaction product;
optionally, reacting the imidazole-substituted aminophenol ligand compound shown in the formula (II) with a zinc metal raw material compound in an organic medium at a reaction temperature of 0-100 ℃ for 12-96 hours, and collecting a target imidazole-substituted aminophenoxy zinc complex (I) from a reaction product;
substituent R in the preparation method 1 ～R 4 Is consistent with each corresponding group of the imidazole-substituted aminophenol ligand (II) and the metal zinc complex (I) thereof which meet the requirements of the invention;
the zinc metal raw material compound has a general formula of ZnX 2 X is consistent with the corresponding group of the imidazole-substituted aminophenoxy zinc complex (I) which meets the invention; the zinc metal starting compound is preferably bis { di (trimethylsilyl) amino } zinc;
the molar ratio of the imidazole substituted aminophenol ligand compound to the zinc metal raw material compound is 1:1-1.5;
in the preparation method, the organic medium is one or two selected from methanol, tetrahydrofuran, diethyl ether, toluene, benzene, petroleum ether and n-hexane.
4. The polymerization process of claim 1 wherein the 1, 3-dioxolan-4-one compound has a structure according to formula (VIII):
Figure FDA0004123037720000021
in the formula (VIII):
the R is 7 Independently selected from C 1 ～C 12 Alkyl of straight, branched or cyclic structure, C 7 ～C 20 Mono-or poly-aryl substituted alkyl, C 6 ～C 18 Aryl of (a);
the R is 8 、R 9 Independently selected from C 1 ～C 6 Alkyl groups of straight, branched or cyclic structure, or both are linked to form a ring; r is R 8 And R is 9 May be the same or different;
* The configuration of the carbon atom at which the standard is positioned is R-, S-or racemization structure.
5. The polymerization process of claim 4 wherein in said formula (VIII), said R 7 Independently selected from C 1 ～C 6 Alkyl, phenyl, benzyl of straight, branched or cyclic structure; the R is 8 、R 9 Independently selected from methyl, ethyl and propyl, or the two are connected to form a five-membered ring and a six-membered ring.
6. The polymerization process according to any one of claims 1 to 5, wherein the 1, 3-dioxolan-4-one compound has a structure represented by the formulas (IX) to (XII):
Figure FDA0004123037720000031
7. the polymerization process according to claim 1, wherein the starting material for the polymerization reaction further comprises lactide as comonomer; the lactide is one or more of L-lactide, D-lactide, rac-lactide and meso-lactide.
8. The polymerization process according to claim 1, wherein the ratio of the imidazole-substituted aminophenoxy zinc complex catalyst to the amount of 1, 3-dioxolan-4-one compound and lactide is 1 (50 to 1000): 0 to 1000.
9. The polymerization process according to claim 1, wherein the polymerization reaction temperature is 25 to 160 ℃; the polymerization time is 0.1 to 200 hours.
10. The polymerization method according to any one of claims 1 to 9, wherein the raw material for the polymerization further comprises an alcohol compound; the alcohol compound is C 1 ～C 10 Alkyl alcohols of linear, branched or cyclic structure, or C 7 ～C 20 Mono-or poly-aryl substituted alkyl alcohols; the ratio of the imidazole substituted aminophenoxy zinc complex catalyst to the mass of the alcohol compound is 1 (0-10).
CN202310237809.5A 2023-03-14 2023-03-14 Polymerization method of 1, 3-dioxolan-4-one compounds Pending CN116217909A (en)

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